Zirconium oxide-silicon oxide silver catalyst support and process using the same



' iactured from ethylene oxide.

Patented Apr. 15, 1952 ZIRCONIUMI OXIDE-SILICON OXIDE SILVER CATALYST SUPPORT AND PROCESS USING THE SAME William E. Burt and Janet T. Burt, Pleasant Ridge, and Waldo B. Ligett, Berkley, Mich., assignors to Ethyl Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 9, 1950,

Serial No. 200,107

3 Claims.

This invention relates to a support for a catalyst useful in the oxidation of olefins. In particular our invention relates to a catalyst support for the oxidation of ethylene to ethylene oxide. Our invention is also directed to a process for the oxidation of ethylene using silver deposited on such support. Ethylene oxide is an important chemical intermediate, being employed commercially in many processes. For example, acrylonitrile can be manufactured by treating ethylene oxide with hydrogen cyanide. Hydrolysis of ethylene oxide to ethylene glycol results in an important antifreeze compound. Likewise, from ethylene glycol can be prepared dinitro glycol for dynamite. Furthermore, ethanolamines, resins, poly mers, aldehydes and glycol ethers can be manu- By treating the oxide with alkyl phenols important detergents can be manufactured, etc. Finally ethylene oxide finds commercial use itself as a solvent and fumigant.

It is well known that silver catalyzes the oxidation of ethylene, by means of air or oxygen, to ethylene oxide. Of the many catalysts proposed for this reaction, only silver has been proved in practice to possess suiiicient activity and selectivity to merit consideration in a commercial operation. However, for successful com mercial operation such catalyst must remain active over long periods of use, must be insensitive to changes of temperature, and must be relatively insensitive to impurities present in the reactants. Silver metal, used alone, fails to satisfy 7 these requirements. In addition, the conversion of ethylene to ethylene oxide must be high and the formation of by-products, or products of competing reactions must be minimized in order that the manufacturing process be economically attractive. Silver alone produces extremely small yields of ethylene oxide and uneconomically high yields of acetaldehyde, carbon dioxide and water.

Various means have been proposed to overcome these disadvantages, such as incorporating an inert material with the silver, With Iimited success. Most of these expedients produce a catalyst which suffers from one or more of the disadvantages inherent in the silver alone. In addition, control of the reaction, because of poor heat transfer of the supported catalyst makes the reaction temperature more diflicult to control, resulting in an increased proportion of undesirable products, or requiring complicated reactors with internal cooling iacilities. To be 2. commercially acceptable it is preferred that a catalyst be supported on a material which can be utilized in a fluidized condition. Many supports which can be utilized in a thermally inefficient fixed-bed reactor cannot be satisfactorily fluidized, and agglomerate, channel, or slug" when fluidized operation is attempted.

-Furthermore, a catalyst for the oxidation must attain its maximum activity within a reasonable period of operation.

It is, accordingly, an object of this invention 7 to provide a support material for silversuch that ethylene oxide can be produced by the direct oxidation of ethylene in its presence and an improved yield obtained thereby. An additional object is to provide a supported silver catalyst which retains maximum activity over long periods, to produce a high yield of ethylene oxide over a broad range of temperatures, and is not destroyed by accidental exposure to obnormally high temperature. It is a further object of this invention to provide a catalyst support for the manufacture of ethylene oxide whereby the activity of the catalyst reaches a Y maximum after a short period of operation. As

* reaction, and minimize the side and secondary reactions. Other objects of our invention will appear from the further description hereafter.

' We obtain the advantages of our invention by incorporating silver with a refractory material comprising zirconium oxide and silicon oxide. More particularly our invention comprises a crushed refractory material having a composition which can be expressed as 30 to per cent zirconium oxide and 70 to 30 per cent silicon oxide, the balance if any inert organic oxides. However, our preferred support is a spinel type material corresponding to the formula ZrOz.SiOz. The conventional amount of silver is deposited on our support, namely 4 to 50 per cent with the best results being obtained between 4 and 20 per cent.

The temperature of reaction for the process of this invention is between and 400 C. although the normal preferred range is between 250 and 300 C. An important advantage of the support of this invention is that it stands up well at temperatures above 300 C. quently due to poisoning, the silver catalyst loses its activity but the activity can be restored when the temperature is increased above 300 Also misoperation may result in a high temperature which must be withstood by the support. The supports of the prior art are deficient in this respect.

It is also important that the catalytic activity of the support reach a maximum after a short period of operation, in order to increase its usefulness. The support of this invention is excellent in this respect.

The reaction between ethylene andv oxygen proceeds at either atmospheric, subatmospheric or superatmospheric pressures. The proportion of ethylene and oxygen or air (or. other oxygencontaining gas) while not critical should preferably be between 125 and 1:70 parts of ethylene to air.

The silver catalyst on the support used in carrying out the reaction can be disposed in the reaction vessel in any manner provided. the necessary contact time is provided, which is preferably between 5 and minutes. However, one advantage of the catalyst support of this invention is that it is readily adaptable to fluidized technique because it can be readily fluidized. Many supports are difficult and even impossible to fluidize.

Inorder to best fluidize our catalyst and support the catalyst, particle sizes are important. The particles should not be all the same size and it is important that a certain percentage should be small in order to provide a lubricat ing effect. For best results in a fluid operation the particle size mixture should have 30 to 40 partsibetween 100- and 200-mesh, 30 to 40 parts between 200- and, 325-mesh, and 10 to parts smaller than 325-mesh.

It is customary in this art to use promoters in: order to increase the activity of thesilver. While good results are obtained in our process without a promoter, for best results one of the following promoters should be used: BaOz, CaOz, BaCQs, benzoyl peroxides and. generally the oxides, carbonates, hydroxidesand peroxides of the alkali andalkaline earth metals. However, we prefer to use barium oxide, BaOz, as the promoter.

Thesupport and catalyst may be prepared and used in any suitable manner as that generally described in the article by McBee, Hass, and

Wiseman, Industrial and Engineering Chemistry,

3'7; 432 (1945). However since it is preferred to use the catalyst in a fluidized operation the procedure best suited for such operation will be described although it is to be understood that our invention is not so limited.

Thesupport material to be tested is first mixed in the proper proportion and then sized by screening with standard screens of 100-, 200-,

and 325-mesh. The different particle sizes falling within the above mesh sizes are then mixed with silver oxide and distilled water thereby forming a slurry. The slurry is heated while agitating to a temperature of about 120 C. until the catalyst is thoroughly dried. After such drymg, each size of catalyst is rescreened and the desired portions of each size are mixed and the catalyst-is ready for use in the fluidized reactor.

The invention can be best understood by referring to the following working example.

A catalyst was prepared containing 11.3 per cent silver, 2 per cent of a promoter, BaOz, on a support comprising equal parts of. zirconium oxide and silicon oxide (Z1O2.Si02). As to the particle size, the mixture consisted of 35 parts between 100- and ZOO-mesh, 35 parts between 200- and 350-mesh, and 30 parts less than 325-mesh. To a reactor" suitable for fluidized operation and containing 100 parts of catalyst, were continuously introduced 10 parts of air to 1 part of ethylene. The reaction temperature was maintained at 263 C. and the pressure was atmospheric. The reaction products were continuously separated from the catalyst. The catalyst reached its maximum activity quickly and after 410 hours ofoperation the conversion to ethylene oxide was 43.3 per cent with 84 per cent of the ethylene reacting.

To demonstrate the thermal stability of the support, the temperature was raised to 310 C. for 24 hours and the conversion was the same after. the temperature was again 263 C. After 2500 hours operation the conversion to ethylene oxide was 43.4 per cent.

Within the limits heretofore set forth variation in per cent of zirconium oxide and silicon oxide, particle size, and temperature range resulted in conversions to ethylene oxide between and per cent. When a promoter such as barium oxide is not employed the yields are from 10 to 15 per cent less than whenusing a promoter. Variations in silver content have very little eilectv on the yields.

Having described and illustrated our invention, other embodiments within thev scope of the following claims are readily apparent to one skilled in the art.

We claim:

1. A thermally stable oxidation catalyst containing silver and a support and capable of being readily fluidized, said support consisting essentially of about 30 to '70 per cent zirconium oxide and about '70 to 30 per cent silicon oxide, and of a particle size mixture comprising 30 to 40 parts between and ZOO-mesh, 30 to 40 parts between 200- and 325-mesh, and 10 to 35 parts smaller than 325-mesh.

2. The support of claim 1 which corresponds to the formula ZrOaSiOz.

3. A fluidized process for making ethylene oxide comprising reacting ethylene with air in the presence of the catalyst of claim 1 at a temperature between about and about 400 C.

REFERENCES CITED The following references are of record. in the file of this patent:

UNITED STATES PATENTS Name Date Becker Nov. 11, 1947 Number 

1. A THERMALLY STABLE OXIDATION CATALYST CONTAINING SILVER AND A SUPPORT AND CAPABLE OF BEING READILY FLUIDIZED, SAID SUPPORT CONSISTING ESSENTIALLY OF ABOUT 30 TO 70 PER CENT ZIRCONIUM OXIDE AND ABOUT 70 TO 30 PER CENT SILICON OXIDE, AND OF A PARTICLE SIZE MIXTURE COMPRISING 30 TO 40 PARTS BETWEEN 100- AND 200-MESH, 30 TO 40 PARTS BETWEEN 200- AND 325-MESH, AND 10 TO 35 PARTS SMALLER THAN 325-MESH.
 3. A FLUIDIZED PROCESS FOR MAKING ETHYLENE OXIDE COMPRISING REACTING ETHYLENE WITH AIR IN THE PRESENCE OF THE CATALYST OF CLAIM 1 AT A TEMPERATURE BETWEEN ABOUT 150* AND ABOUT 400* C. AND WITH A ETHYLENE TO AIR RATIO OF BETWEEN ABOUT 1:5 AND 1:7. 